Thiadiazolyl-azo-{60 -naphthylamine compounds

ABSTRACT

Monoazo compounds consisting of a 1,3,4-thiadiazolyl diazo nucleus and an Alpha -naphthylamine coupling nucleus are particularly useful for dyeing carpets of nylon fibers on which the compounds produce red to violet shades.

United States Patent Weaver et al.

[451 Apr. 15, 1975 THIADIAZOLYL-AZO- a-NAPl-lTl-IYLAMINE COMPOUNDS lnventors: Max Allen Weaver; Herman Speight Pridgen, both of Kingsport, Tenn.

Assignee: Eastman Kodak Company,

Rochester, NY.

Filed: July 2, 1973 Appl. No.: 376,049

U.S. Cl 260/158; 8/41 B; 260/326.5 C;

260/326.5 L Int. Cl C09b 29/06; D06p 1/18; D06p 3/26 Field of Search 260/158 [56] References Cited UNITED STATES PATENTS 3,084,153 4/1963 Fishwick et a1 260/158 3,631,020 12/1971 Weaver et al 260/158 Primary Examiner-Floyd D. l-ligel Assistant ExaminerC. F. Warren [57] ABSTRACT 3 Claims, N0 Drawings THlADlAZOLYL-AZO-a-NAPHTHYLAMINE COMPOUNDS This invention relates to certain novel azo compounds useful for dyeing polyamide fibers and, more particularly, it relates to 1,3,4-thiadiazolyl-azonaphthylamine compounds and to poly-amide fibers dyed therewith.

Our novel azo compounds have the general formula R is hydrogen; alkyl of one to about eight carbon atoms; lower alkylthio substituted with hydroxy, lower alkanoyloxy, succinimido, 2-pyrrolidinono, lower alkanoylamido. lower alkoxy. cycloalkyl or aryl; cyclohexylthio; lower alkylcyclohexylthio; lower alkanoylamido, chlorine, bromine; or aryl; and

R is hydrogen; alkyl of one to about eight carbon atoms; lower alkyl substituted with formamido, lower alkanoylamido, 2-pyrrolidinono, lower alkoxy, hydroxy, hydroxy-lower-alkoxy, carbamoyl, lower alkylcarbamoyl, aryloxy, aryl, cyclohexyl, lower alkanoyloxy. lower alkoxycarbonyl, succinimido, phthalimidino, lower alkylsulfonamido. lower alkylthio, arylthio, or lower alkoxycarbonylamido; aryl; cyclohexyl; cyclohexyl substituted with lower alkyl; or furfuryl;

in which each aryl moiety is phenyl or phenyl substituted with lower alkyl, lower alkoxy, chlorine or bromine.

The compounds of our invention are prepared by diazotizing an aminothiadiazole having the formula and coupling the resulting diazonium salt with an a-naphthylamine having the formula according to conventional procedures. The aminothiadiazoles are obtained by published procedures or techniques analogous thereto. The a-naphthylamines are prepared by the alkylation of a-naphthylamines, by the reductive alkylation of l-nitronaphthalene with aldehydes and ketones or by reacting primary amines with a-naphthols according to the Bucherer reaction.

Our novel azo compounds produce red to violet shades on nylon fibers. The compounds are particularly suitable for dyeing carpets of nylon fibers on which the compounds exhibit good to excellent fastness to light, gas, ozone, sublimation and crocking. The compounds also exhibit good dyeability and migration properties. This unique combination of properties distinguishes our novel compounds from the compound 4-(5-phenyl- 1,3 ,4-thiadiazol-2-ylazo l -amino-5-naphthol.

As used herein to describe an alkyl moiety of a group represented by R or R lower designates a carbon content of one to about four carbon atoms. Preferred aryl moieties of the aryl-moiety containing groups included in the above definitions of R and R are tolyl, anisyl, ethoxyphenyl and chlorophenyl. The substituted alkylthio groups which R can represent preferably are cyclohexylmethylthio, benzylthio, phenethylthio or a group having the formula SXR in which X is ethylene, propylene, trimethylene, or tetramethylene and R is hydroxy, lower alkanoyloxy, succinimido, lower alkanoylamido, or lower alkoxy. Preferred substituted alkyl groups represented by R are benzyl, phenethyl, cyclohexylmethyl, carbamoylethyl, lower alkylcarbamoylethyl or a group having the formula -XR in which X is ethylene, propylene, trimethylene or tetramethylene and R is hydroxy, lower alkoxy, lower hydroxyalkoxy, formamido, lower alkanoylamido, 2-pyrrolidinono, phthalimidino, lower alkoxycarbonylamido, lower alkylsulfonamido, succinimido, lower alkanoyloxy, lower alkoxycarbonyl, aryloxy, lower alkylthio, or arylthio.

A group of our novel compounds which are especially preferred because of their costzperformance ratio are those of Formula (I) in which R is hydrogen, lower alkyl or lower alkylthio and R is cyclohexyl, lower alkyl, carbamoylethyl or a group having the formula XR in which X is ethylene, propylene or trimethylene and R is hydroxy, formamido, lower alkanoylamido, lower alkylsulfonamido or lower alkoxy.

Our novel azo compounds and their synthesis and use are further illustrated by the following examples.

EXAMPLE l A mixture of l-naphthol (28.8 g.), N-(?.- aminoethyl)-2-pyrrolidinone (76.8 g.), sodium bisulfite (20.8 g.), and water 170 ml.) is heated in an autoclave at 155C. for 12 hours. The solid thus produced is collected by filtration and recrystallized from ethanol. The yield is 37.4 g. of N-[2-(2-pyrrolidinono)ethyl]-lnaphthylamine, a white solid which melts at l37-l39C.

Anal. Calcd. for C H N Oz C, 75.7; H, 7.2; N, 11.0. Found: C, 75.7; H, 7.2; N, 11.0.

EXAMPLES 2-11 Sodium nitrite is added gradually to 25 ml. concd.

v H- ,SO The solution is cooled and ml. 1:5 acid (1 (Exam- 4 with occasional stirring. they are diluted with water to precipitate the azo products. The products are colreslurried in hot methanol. The azo compounds obtained produce fast violet shades on nylon carpet.

The azo compounds set forth in the examples of the following Table conform to Formula (I) and are prepared according to the procedures described hereinabove. The color given for each of the azo compounds set forth in the Table refers to the shade it produces on nylon fibers. Examples 2 through 12 of the Table give the structures of the azo compounds prepared in the lected by filtration. washed with water. dried in air. and 10 examples set forth above.

Example No. R a c 1 g1;

2 c,H,s- -c,n, Violet 3 c,n,s- -c.a, 1 Violet 4 V cans -ca,cu m1cocn, Violet s c,a,s- -ca,cir,u' cm) ,co Violet 6 C=H=S I -(CH,),0CH, Violet 7 C,H,S- CH, Violet s c,u,s- -Cfl=CH=Ol-1 Violet 9 c,a,s- -cn,ca,ocu,cu ,oa Violet 1o c,u,s- -cu,cu,comr, Violet:

11 c,n,s- -cu(ca,)c,n, Violet 12 c,u,s- -cu,cn,ocn,cn,ocn, Violet 13 c,a,s- -cu,cn,oc,u, Violet l4 C=H,S- -CHCH,CH, Violet 1 5 C=H,S- 478 6.5, Violet l6 C=H,S- -CH,C.H.-p-OCH, Violet 17 c ,u,s- -cu,c.n.-- -cu, Violet 1a c,u,s- -cu,c.n", Violet 19 c,n,s- -cn,cn,com1cu(cn, Violet =H,s- --cu,t:1i,cooc,1i Violet 21 =H,S -cu,cn(on)cu,ou Violet '22 =H= 'ci i,cn(ou)cu, Violet:

23 c,u,s- -ca,cn(on)'cn,ocu Violet 24 cnus- 4mm Violet 25 cu,s- -cn,cu,micocu Violet 26 cu,s- -c,n, Violet '27 cu,s- -cn cn, c,n, Violet:

2a ca,smagma (mo Violet 29 cuss- (C11,) ,ocn(c n,' Violet 3o cu,s- (cu,) ,ocn,cu,ocn, Violet 31 cn,s- --(c1i,),oc.u Violet 32 ClhS- (CH2) :NHCOH Violet Example No.

Color Violet Violet Violet Violet Violet Violet Violet Violet Violet Violet Violet Violet Violet Violet Violet Violet Red Red

Red

Red

Red

Red

Red

Red

Violet Violet Violet Violet.

Violet Violet Violet Violet Violet Violet Violet Violet Red Violet The novel azo compounds can be applied to polyamide textile materials according to known disperse dyeing techniques. Various dispersing and wetting agents can be employed in the dispersion of the finely divided dye compound in an essentially aqueous dyebath. Procedures by which the compounds of the invention can be applied to polyamide textile materials are described in U.S Pat. Nos. 3.l00,l34 and 3,320,021. The follow-' ing example illustrates a method for applying the novel compounds to polyamide fibers.

EXAMPLE 71 The azo compound (16.7 mg.) of Example 2 is dispersed in 10 cc. of 2-methoxyethanol. A small amount (3-5 cc.) of a 3 percent sodium lignin sulfonate solution is added, with stirring. and then the volume of the bath is brought to 150 cc. with water. A 5 g. textile fabric made of nylon 66 fibers is placed in the bath and worked minutes without heat. The bath is then slowly brought to the boil over a -minute period and the dyeing is carried out at the boil for 1 hour. The dyed fabric is then removed from the dyebath, rinsed with water and dried in an oven at 250F. The fabric is dyed a bright shade of violet exhibiting excellent fastness properties when tested in accordance with the procedures described in the Technical Manual of the American Association of Textile Chemists and Colorists, 1968 edition.

The polyamide materials which can be dyed with the novel azo compounds are well known and include nylon 66 (polyhexamethylene adipamide) manufactured by the polymerization of adipic acid and hexamethylenediamine, nylon 6 (polycaprolactum) prepared from epsilon-aminocaproic acid lactum (cawherein R is hydrogen; alkyl of one to eight carbon atoms;

lower alkylthio substituted with hydroxy, lower alkanoyloxy. succinimido, Z-pyrrolidinono, lower alkanoylamido, lower alkoxy. cyclohexyl, phenyl, or phenyl substituted with lower alkyl, lower alkoxy, chlorine or bromine; cyclohexylthio; lower alkylcyclohexylthio; lower alkanoylamido; chlorine; bromine; or aryl; and i R is hydrogen; alkyl of one to eight carbon atoms;

lower alkyl substituted with formamido, lower alkanoylamid'o'. 2-pyrrolidinono, lower alkoxy. hydroxy, hydroxy-lower-alkoxy, carbamoyl. lower alkylcarbamoyl, aryloxy, aryl, cyclohexyl, lower alkanoyloxy, lower alkoxycarbonyl. succinimido. phthalimidino, lower alkylsulfonamido, lower alkylthio, arylthio, or lower alkoxycarbonylamido; aryl; cyclohexyl; cyclohexyl substituted with lower alkyl; or furfuryl; in which each aryl moiety is phenyl or phenyl substituted with lower alkyl, lower alkoxy. chlorine or bromine. 2. A compound according to claim 1 wherein R is hydrogen; alkyl of one to eight carbon atoms; cyclohexylmethylthio; benzylthio; phenethylthio; cyclohexylthio; lower alkylcyclohexylthio; lower alkanoylamido; chlorine; bromine; aryl; or a group having the formula SXR in which X is ethylene, straight or branch chain trimethylene or tetramethylene and R is hydroxy, lower alkanoyloxy, succinimido, lower alkanoylamido. or lower alkoxy; and R is hydrogen; alkyl of one to eight carbon atoms;

benzyl; phenethyl; cyclohexylmethyl; carbamoylethyl; lower alkylcarbamoylethyl; a group having the formula X-R in which X is ethylene, straight or branch chain trimethylene or tetramethylene and R is hydroxy, lower alkoxy, lower hydroxyalkoxy, formamido, lower alkanoylamido, 2- pyrrolidinono, lower alkoxycarbonylamido. lower alkylsulfonamido succinimido, phthalimidino, lower alkanoyloxy, lower alkoxycarbonyl, aryloxy, lower alkylthio or arylthio; aryl; cyclohexyl; cyclohexyl substituted with lower alkyl; or furfuryl. 3. A compound according to claim 1 wherein R is hydrogen, lower alkyl or lower alkylthio; and R is cyclohexyl, lower alkyl; carbamoylethyl, or a group having the formula XR in which X is ethylene, or straight or branch chain trimethylene and R is hydroxy, formamido, lower alkanoylamido, lower alkylsulfonamido or lower alkoxy. 

1. A COMPOUND HAVING THE FORMULA
 2. A compound according to claim 1 wherein R1 is hydrogen; alkyl of one to eight carbon atoms; cyclohexylmethylthio; benzylthio; phenethylthio; cyclohexylthio; lower alkylcyclohexylthio; lower alkanoylamido; chlorine; bromine; aryl; or a group having the formula -S-X-R3 in which X is ethylene, straight or branch chain trimethylene or tetramethylene and R3 is hydroxy, lower alkanoyloxy, succinimido, lower alkanoylamido, or lower alkoxy; and R2 is hydrogen; alkyl of one to eight carbon atoms; benzyl; phenethyl; cyclohexylmethyl; carbamoylethyl; lower alkylcarbamoylethyl; a group having the formula -X-R4 in which X is ethylene, straight or branch chain trimethylene or tetramethylene and R4 is hydroxy, lower alkoxy, lower hydroxyalkoxy, formamido, lOwer alkanoylamido, 2-pyrrolidinono, lower alkoxycarbonylamido, lower alkylsulfonamido, succinimido, phthalimidino, lower alkanoyloxy, lower alkoxycarbonyl, aryloxy, lower alkylthio or arylthio; aryl; cyclohexyl; cyclohexyl substituted with lower alkyl; or furfuryl.
 3. A compound according to claim 1 wherein R1 is hydrogen, lower alkyl or lower alkylthio; and R2 is cyclohexyl, lower alkyl, carbamoylethyl, or a group having the formula -X-R4 in which X is ethylene, or straight or branch chain trimethylene and R4 is hydroxy, formamido, lower alkanoylamido, lower alkylsulfonamido or lower alkoxy. 